Removal and recovery of benzol and naphthalene from gases



REMOVAL AND RECOVERY OF BENZOL AND NAPHTHALENE FROM GASES Filed Jan. 25, 1934 Patented Sept". 13,1933

anni? amarsi v Adair Schwalenber/ch, Essen, Germany, assigner, by mesne assignments. to Kappers Company, a.

corporation ai Delaware v Application January 25,. 11934, Seriali No. iildldll En Germany January 25, i033 il Claim.

The object oi the present invention is to provide such improvements in the removal and recovery of benzol, its homologues and naphthalene from gases, particularly coal distillationgases, that the removal of the said' substances from the lgas can. be effected. in a single operation and benzol and homologues and naphthalene on the other hand can be recovered separately in practically pure condition.

Normal coal distillation gas contains, after the usual so-called iinal cooling and before ythe scrubbers serving to remove benzoLabout V grammes benzol and homologues per cubic meter and about 0.4 to 0.6 gramme naphthalene. For the removal of benzol and homologues the gas l is Washed with a usual washing oil. The used washing oil is subjected to steam distillation. The vapors f distillation thus produced contain about equal quantities by Weight of washing oil and benzol, i. e. about 50% benzol and homologues and about 2% naphthalene. From the condensate of the steam distillation benzol and homologues are removed by rectiiicatlon, whilst the naphthalene-containing oil remains behind. As the quantity of the napl'ithalene in the residual oil, as stated, only amounts to about 2%, it is not possible to separate the naphthalene from the oil by crystallization whilst cooling to temperatures still obtainable, having due regard to favorable economy, Without'artiiicial cooling; Consequently the Washing oil becomes enriched with naphthalene, which in the usual manner is used in circulation for renewed Washing 'of benzol from the gas, gradually to such a quantity that the vapor pressure of the Washing oil in connection with naphthalene is in equilibrium with the vapor pressure of the gas as regards naphthalene. In the case of normal Washing oil this point lies at about 12% naphthalene. Beyond this point an enriching of the washing oil with naphthalene is not possible in the method of operation hitherto usual.' But even with a content of naphthalene of 12% the naplithalene cannot be recovered from the washing oilI without artiiicial cooling.

According to the present invention the separation both of benzol and of naphthalene from the washing oil, which served for bothl the removal ci benzol and homologues and also naphthalene from the gases, isrendered fundamentally possible. in that the condensates derived from dis-v tilling the Washingoil, coming irom thescrubber, in the steam distillation step is subjected before the rectication to a. pre-distillation for the recovery of benzol and homologues, which is carried p out at such a temperature that the heavier constituents of the washing oil remain behind, Whilst the lighter constituents ci' the washing oil together with benzol, its homologues and naphthaiene are evaporated. The. vapors produced by this pre-distillation are then conducted Ainto the rectihcaticn apparatus including a still for distillation of benzol and homologues, from which there is withdrawn, after driving off benzol and homologues, an oil with a content of about 30% naphthalen'e. From 'this part of the distillation step oil highlyenri'ched with naphtlialene is produced and there can be separated a very pure naphthalene by crystallization with cooling to room' temperatures above 10 C. which can be obtained directly Without artiilcial cooling.

Ilihe quantity of heavy constituents of washing oil which occurs in the pre-.distillation step ac' coi-ding to the invention varies. 1n general .itamounts to about 30 to 90% of the condensed oil containing benzol and naphthalene introduced into the pre-distillation apparatus in the case when the main quantity of naphthalene is to be separated i'rom the heavier constituents of the washing oil in the pre-distillation stage.

aThe heavier constituents oi thevvashln'g oil remaining inthe pre-distillation stage, are mixed with the lighter constituents, which remain in the main distillation stage, after the naphthalene hasbeenseparated from the lighter constituents by cooling, and then are again used together-for washing benzol and naphthalene from the gas.

The invention will now be described with` reierence to the accompanying drawing showing,

partly in elevation and partly in cross section,Vv

apparatus for practicing the invention.

En the arrangement shown in the drawing used washing oil, containing benzol and naphthalene, from the container i, of which the function is described hereinafter, is supplied through a pipe line 2 by means of a pump t to a heating device fi. "llhe hot Washing oil andthe vapors producedv during the heating pass from the device il through the pipe lines d and 0 into a firnovvn primary distilling column apparatus '71. This column apparatus i has a series of bottoms or trays which are `provided'vvith vvapor openings 0 covered by bells' d, and at the middle each has a liquid overow i0. SteamV is introduced into the bottom of the-column apparatus through the pipe line i i.

uents condensed bottoms of the column apparatus,` whilst the washing oil ows downwardly in the apparatus 'l from top to bottom through the openings, l0. Steam and washing oil in this manner come into intimate Contact with one another, whereby the washing oil is heated. The vapors produced in the column apparatus l such as steam, benzol, its homologues, naphthalene and some oi the wash oil, escape through the pipe line i2 and pass into a condensing device i3 where they are cooled. The liquid condensates thus formed new through the pipe line i into a separating tanl: l5. In the separating tank i0 the water escaping from the apparatus 'i separates from the oily substances. The latter are withdrawn at the upper end of the separating tank iii through the pipe line iii, whilst the water passes through the pipe line il' into the tank i0.

, The oily constituents are now conducted through the pipe line i0 into the still i0. To the still l0 there are also supplied through the pipe line 20 those gaseous constituents which were not condensed in the condensing device i3.

Into the lower part of the still i0 there is supplied through the pipe lines 2i steam which in the interior of the apparatus flows through ypipe coils or the like not shown in the drawing. The condensedwater is withdrawn from these heating pipe coils through the pipe lines 22. liquid in the still l0 is thus heated indirectly. The vapors thus formed, benzoi, its homologues, naphthalene, and a small part of the wash oil vapor condensed from the still it, rise and pass through the pipe line 23a into the dephlegmator part 23 oi the apparatus l0, maintained atl a predetermined temperature, from which they escape through'the pipe line 2d after passing a separating bottle 2155 for separating the constitin the dephlegmator. The condensate from the separating bottle 2t flows through the pipe line bach into the still iS.

For coolingthe dephlegmator there is preferablyused cold water which flows to a cooling pipe sys tem, located in the interior of the dephlegmator '23, through a pipe line 2li and flows out through a pipe line 2t.

The oil which is not evaporated in the still it) and which mainly consists of the heavier constituents of the washing oil and is practically free from naphthalene, is withdrawn through the pipe line 20.

The vapors produced in the still iii pass through the pipe line 25 into the main distillatenor of the apparatus 32 and ilows out throughl the pipe line 3&3. 'I'hecondensates formed in the apparatus 32 are withdrawn from the lower part of the apparatus through the pipe lines 05.

The liquid constituents which are not evapof rated in the main distillation still 30 'ow through the lpipe line 36 to a naphthalene crystallizing pan 31 in which they are cooled to about room temperature but above C. As a result solid crystalline naphthalene separates from the liquid which contains about 30% naphthalene. The residual liquid passes from the device 31 through the pipe line 38 into the storage tank 39 for the Thelene per 100 cubic meters.

amener washing oil to be re-used for washing out benzol and-naphthalene. Tothe pipe line 38 is also con` nected the pipe line 29 so that thus-the whole of the washing oil freed. from benzol, its homologues and naphthalene, which was driven oi in the column apparatus li, is again continued.

There will now be described the path followed by the used washing oil which is treated in the apparatus shown in the drawing. The used washing oil withdrawn from the scrubbers, not shown in the drawing, which serve for washing benzol, its homologues and naphthalene from the gas. is conducted to a storage tank 0. From this it ows through the pipe line M into the cooling pipe system ci the condensing device i3 in which it is used for cooling the vapors escaping from the column apparatus l, vin this manner there is obtained simultaneously an advantageous preheating of the cold used washing oil. The washing oil thus preheated then passes through the pipe 02 into the tank i, which simultaneously serves as storage tanh and as heat exchanging apparatus. rThe used crude washing oil is here further preheated, the hot unvaporizecl washing oil from the column still l here serving for the preheating. For this purpose there is connected to the bottom oi the column apparatus 'E the pipe line 03 through which the hot Washing oil ows from l into a pipe system located in the in, terior oi the tank i. in the tank i the hot residual oil of the column apparatus i imparts a portion of its heat to the colder untreated washing oil. rlhe residual oil pre-cooled in this manner then ilows through the pipe line ld into a pipe ,cooling apparatus Q55, sprayed with wat/er from which it passes through the pipe line il@ into the storage tank 30 for fresh washing oil. The regenerated wash oil is pumped continuously inI cycle baci; to the gas-washing benzol-scrubber (not shown) through a pipe line 39a. At certain intervals part of the wash oil, circulating from the benzol scrubber to the distillation plant and thence to the tanlr 30 for return back to the benzoi scrubber, must be replaced by new or fresher wash oil to replacedeterioration. The added oil may be introduced into tank 3s, or at any other point in the cycle of flow ofthe benzol-absorbent wash oil..

The process according to the invention isv carried into euect somewhat in the following man- Der'. y

lt is assumed that the gas of a coal distillation plant is to be treated which has an average of i000 metric tons oi dry coal per day. The colcing of this coal produces about 300 cubic meters of gas per ton of coal, that isdaiiy 300,000 cubic meters of gas. After the usual nal cooling of the gas this contains before passing into the ben aol scrubbers about to 60 grammes naphtha.-

In this case there is assumed a naphthalene content of the gas or grammes per cubic meters. lThe quantity of naphthaiene contained in the gas therefore amounts per day. to lkilogrammes. of which kilogrammes are washed out per day by the washing oil.

, nie content of the gas in benzol and its homologues amounts to 25 grammes per cubicA meter, that is per day 7500 kilogrammes benzol and homologues..

According tov experience the quantity of washing oil, which passes over in the column apparatus 1 when driving off bnzol and its homologues in order to obtain a siiicient removal ot benzol and its homologues from the washing 75 unes 4t, at, sind sa now only contains 22,500

on, is the saine as the quantity of benzol driven od. In the example described 7500 kilogrammes of Washing oil are thus distilled over daily in the column apparatus ii. In this quantity of washing oil there is alsoy contained the total naph llfiitinerto `method .of operation,l together Withthe residual oil vfrointhe rectiicationapparatus for benzo'l back' it'o the washing oil which then becomes enriched. This enriching continues until the vapor pressure of the Washing oil with naphthalene is equal to the vapor pressure of the gas with naphthalene. As a Eesult it follows that bythe hitherto usual method of operation naphthalene cannot be washedfrom the gas together with benzol. On the contrary it 'was therefore always necessary to provide beyond the benzol scrubber a separate scrubbery for naphthalene. y

According to the' invention the vapor mixture;

escaping from the column apparatus il, consisting of 7500 kilogrammes benzolandhomoiogues, 6850 kilogrammes .washing oil constituents and fiiikilogrammes naphthalene, is so decomposed that as first fraction there'is obtained a washing oil, which does not contain' more naphthalene than the initial washing oil, as second fraction a washing oil highly enriched with'naphthalene i and as third fraction benzol and its homologues. For this purpose the condensate of the vapor mixture escaping from the column apparatus l is subjected in the pre-distillation stage .it to constituents entering the main distillation apparatus 3d to a distillation at about dii-90 C. measn ured at the outlet oi the distillation vapors at a.

With this methodof operation the residual oil,V ``colle`cting in the pre-distillation stage id and Withdrawn vthrough the. pipe line it, contains 395 kilogrammes of naphthalene per day (=6%) and the residual oil in the main distillation stage 3d, 255 kilogrammes oi naphthalene per day (=2i'.i%l. From the latter residual oil there fare separated in the crystallization device til 150 kilogrammes of naphthaiene per day, v)From kilogrammes oi naphthalene per day equal on an average to 6% naphthalene. This naphtha-- iene content of the washing oil again iiowing back into the'benzol scrubbers remains constant when carrying out the lprocess according tothe invention. It is possible with this constant naphthalene content of the washing oil to remove the naphthalene from the gas up to 5 grammes per 100 cubic metersof gasy during the benzol scrubbing step.v This content of naphthalene in the gas is'so slight that a separate subsequent l` washingout of naphthalene as a rule is unnecessary. Ii", however, for special reasons a stili further reduction of the naphthalene content of the gas should be necessary this is substantially simpler and cheaper as the quantity of naphthalene, remaining in the gas, after the application of the process according to the iny vention, is only very slight.

, in the foregoing the invention has been described with reference to an example for carrying it into eiect, without however, the invention being limited to the method of carrying it out as described. On the contrary the process according to the invention can be modified in various respects without departing from the scope of the following claim. li claim:

v'lihe method of removing and recovering benzoi,`

its homologues and naphthalene from gases con-y taining them, comprising: Washing the gas with wash oil adapted to absorb benzol, its homologues and naphthalene therefrom; heating spent wash oil from the gas washin'gostage to drive oi absorbed benzol, its homologues, naphthalene and a quantity of wash oil about the same as the quantity of benzol, its homologues and naphtha- Iene; condensing the vapors from said heating st'epand pre-distillingl the condensate at about 108 C. to remove benzol, its homologues and naphthalene together with a smal-l portion of the wash oil that comes over with the vaporsfrom the aforesaid heating step; condensing the vapors from the latter pre-distilling step and iinally redistillingthe condensate'at about Bti-90 C. to

l drive off benzol and its homologues leaving as i residuum the naphthalene and wash oil that icomeso'ver. with the vapors from the-pre-disitilling step; separating naphthalene from the latter residuum by atmospheric cooling to room temperature above 10 C.; separating the solid- 

